A Fluorescence-Based Assay System for the Determination of Haloperoxidase-Activity Using a Two-Dimensional Calibration Ap-proach

Screening for an interesting biocatalyst and its subsequent kinetic characterization depends on a reliable activity assay. In this work, a fluorometric assay based on the halogenation of 4-methyl-7-diethylamino-coumarin was established to monitor haloperoxidase-activity. Since haloperoxidases utilize hydrogen peroxide and halide ions to halogenate a broad range of substrates by releasing hypohalous acids, a direct quantification of haloperoxidase-activity remains difficult. With the system presented here, 3-bromo-4-methyl-7-diethylaminocoumarin is preferentially formed and monitored by fluorescence measurements. As starting material and product share similar spectroscopical properties, a two-dimensional calibration ap-proach was utilized to allow for quantification of each compound within a single measurement. To validate the system, the two-dimensional Michaelis-Menten kinetics of a vanadium-dependent chloroperoxidase from Curvularia inaequalis were recorded, yielding the first overall kinetic parameters for this enzyme. With limits of detection and quantification in the low μm range, this assay may provide a reliable alternative system for the quantification of haloperoxidase-activity.     

Nitrous Oxide Adsorption and Decomposition on Zeolites and Zeolite-like Materials

Decomposition of N₂O on modified zeolites, crystalline titanosilicalites, and related amorphous systems is studied by the catalytic and spectroscopic methods. Zinc-containing HZSM-5 zeolites and titanosilicalites with moderate Ti/Si ratios are shown to exhibit a better catalytic performance in N₂O decomposition as compared with conventionally used Cu/HZSM-5 zeolites and amorphous Cu-containing catalysts. Dehydroxylation of the HZSM-5 zeolite by calcination at 1120 K results in an enhancement of the N₂O conversion. The mechanism of the reaction and the role of coordinatively unsaturated cations and Lewis acid sites in N₂O decomposition are discussed on the basis of the spectroscopic data.     

Self-assembled monolayer protection of chiral-imprinted mesoporous platinum electrodes for highly enantioselective synthesis

In modern chemistry, chiral (electro)catalysis is a powerful strategy to produce enantiomerically pure compounds (EPC). However, it still struggles with uncontrollable stereochemistry due to side reactions, eventually producing a racemic mixture. To overcome this important challenge, a well-controlled design of chiral catalyst materials is mandatory to produce enantiomers with acceptable purity. In this context, we propose the synergetic combination of two strategies, namely the elaboration of mesoporous Pt films, imprinted with chiral recognition sites, together with the spatially controlled formation of a self-assembled monolayer. Chiral imprinted metals have been previously suggested as electrode materials for enantioselective recognition, separation and synthesis. However, the outermost surface of such electrodes is lacking chiral information and thus leads to unspecific reactions. Functionalising selectively this part of the electrode with a monolayer of organosulfur ligands allows an almost total suppression of undesired side reactions and thus leads to a boost of enantiomeric excess to values of over 90% when using these surfaces in the frame of enantioselective electrosynthesis. In addition, this strategy also decreases the total reaction time by one order of magnitude. The study therefore opens up promising perspectives for the development of heterogeneous enantioselective electrocatalysis strategies.

Highly enantioselective electrosynthesis with up to 90% ee and short reaction times can be achieved with alkanethiol protected chiral imprinted mesoporous Pt surfaces.     

A 19F NMR Study of the Transmissive Ability of Boron-Containing Bridged Systems with Three- and Four-Coordinated Boron Atoms

Two series of model compounds, Ar₂BOC₆H₄F-4 and Ar₂B(Py)OC₆H₄F-4, containing three-and four-coordinated boron atoms, have been synthesized. It was established by ¹⁹F NMR technique that both systems possess a similar transmissive ability that is in intermolecular coordination with pyridine does not influence the transmissive properties of the boron-oxygen binuclear bridging group. The solvent polarity does not influence the electron transmission in the boron complexes studied.     

Comparison of Proton Acceptor and Proton Donor Properties of H2O and H2O2 in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates

Two new peroxosolvates of drug-like compounds were synthesized and studied by a combination of X-ray crystallographic, Raman spectroscopic methods, and periodic DFT computations. The enthalpies of H-bonds formed by hydrogen peroxide (H₂O₂) as a donor and an acceptor of protons were compared with the enthalpies of analogous H-bonds formed by water (H₂O) in isomorphic (isostructural) hydrates. The enthalpies of H-bonds formed by H₂O₂ as a proton donor turned out to be higher than the values of the corresponding H-bonds formed by H₂O. In the case of H₂O₂ as a proton acceptor in H-bonds, the ratio appeared reversed. The neutral O∙∙∙H-O/O∙∙∙H-N bonds formed by the lone electron pair of the oxygen atom of water were the strongest H-bonds in the considered crystals. In the paper, it was found out that the low-frequency Raman spectra of isomorphous crystalline hydrate and peroxosolvate of N-(5-Nitro-2-furfurylidene)-1-aminohydantoin are similar. As for the isostructural hydrate and peroxosolvate of the salt of protonated 2-amino-nicotinic acid and maleic acid monoanion, the Raman spectra are different.     

Stereoretentive and regioselective selenium-catalyzed intermolecular propargylic C–H amination of alkynes

Herein we report an intermolecular propargylic C–H amination of alkynes. This reaction is operationally convenient and requires no transition metal catalysts or additives. Terminal, silyl, and internal alkynes bearing a wide range of functional groups can be aminated in high yields. The regioselectivity of amination for unsymmetrical internal alkynes is strongly influenced by substitution pattern (tertiary > secondary > primary) and by relatively remote heteroatomic substituents. We demonstrate that amination of alkynes bearing α-stereocenters occurs with retention of configuration at the newly-formed C–N bond. Competition experiments between alkynes, kinetic isotope effects, and DFT calculations are performed to confirm the mechanistic hypothesis that initial ene reaction of a selenium bis(imide) species is the rate- and product-determining step. This ene reaction has a transition state that results in substantial partial positive charge development at the carbon atom closer to the amination position. Inductive and/or hyperconjugative stabilization or destabilization of this positive charge explains the observed regioselectivities.

Selenium catalysis enables a general intermolecular propargylic C–H amination of alkynes. The concerted mechanism gives rise to high regioselectivity for the more electron-rich end of the alkyne and retention of the C–H propargylic stereocenter.